EP2448992B1 - Verfahren zur herstellung von polyether-polyester-blockcopolymer - Google Patents

Verfahren zur herstellung von polyether-polyester-blockcopolymer Download PDF

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Publication number
EP2448992B1
EP2448992B1 EP09846687.3A EP09846687A EP2448992B1 EP 2448992 B1 EP2448992 B1 EP 2448992B1 EP 09846687 A EP09846687 A EP 09846687A EP 2448992 B1 EP2448992 B1 EP 2448992B1
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group
glycol
process according
polyether
acid
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French (fr)
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EP2448992A1 (de
EP2448992A4 (de
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Zhaoqing Liu
Daobing Lin
Qiaobo Li
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Solvay China Co Ltd
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Solvay China Co Ltd
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/81—Preparation processes using solvents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents

Definitions

  • the present invention relates to a process for producing a polyether-polyester block copolymer.
  • the present invention relates to a process for producing a polyether-polyester block copolymer with a di(C 1 -C 4 )alkyl ester of aromatic dicarboxylic acid, an aliphatic diol or aliphatic polyol and a polyether having at least one terminal hydroxyl group in an inert solvent.
  • a di(C 1 -C 4 )alkyl ester of aromatic dicarboxylic acid an aliphatic diol or aliphatic polyol
  • a polyether having at least one terminal hydroxyl group in an inert solvent are also described.
  • Polyether-polyester block copolymers have been used in fabric mill treatment and in both powder and liquid detergents as soil releasing polymers (SRP).
  • SRP soil releasing polymers
  • PET/POET polyethylene terephthalate/ polyoxyethylene terephthalate
  • These copolymers are described in US Patents No. 3416952 , 4349688 , 4702857 , 4877896 , 4738787 , and 5786318 etc.
  • a conventional process for producing such a copolymer employs an aromatic dicarboxylic acid dialkylester and an aliphatic diol as key raw materials.
  • This process usually requires the presence of excessive diol such as ethylene glycol or propylene glycol which is used as a solvent to prevent the aromatic dicarboxylic acid dialkylester from sublimation.
  • the subsequent removal of excessive diol in order to carry out condensation reaction requires high temperature and very low pressure for an extended reaction time as the boiling point of the diol is high and the diol residue is bonded covalently to the aromatic dicarboxylic acid by an ester bond.
  • An example is shown below, starting with dimethyl terephthalate (DMT) to produce a triblock copolymer of polyethylene terephthalate end-capped with methoxy polyethylene glycol (MPEG):
  • DMT dimethyl terephthalate
  • MPEG methoxy polyethylene glycol
  • the present invention is directed to a process for producing a polyether-polyester block copolymer, comprising:
  • (C 1 -C 4 )alkyl means a monovalent saturated straight chain or branched hydrocarbon group having 1-4 carbon atoms.
  • di(C 1 -C 4 )alkyl ester of aromatic dicarboxylic acid means a dicarboxylic di(C 1 -C 4 )alkyl ester in which the two carboxylic ester groups are each directly bound to a carbon atom of an aromatic group.
  • the aromatic group may contain one or more aromatic rings which may be fused or unfused, and the two carboxylic ester groups may be bound to one or two different aromatic rings.
  • the aromatic group may further be substituted by one or more other groups which do not interfere with the transesterification reaction and the polycondensation reaction, such as alkyl or alkylene.
  • aliphatic diol means an aliphatic hydrocarbon compound having two hydroxyl groups in the molecule
  • aliphatic polyol means an aliphatic hydrocarbon compound having at least three hydroxyl groups in the molecule
  • inert solvent means a solvent which does not interfere with the transesterification reaction of step (a) or step (b).
  • the inert solvent is used to prevent the di(C 1 -C 4 )alkyl ester of aromatic dicarboxylic acid from sublimation because such sublimation would generate solid crystalline materials, which disrupts the process.
  • the solvent would also help drive out alcohol by-product of lower boiling point, which will shorten the process time for making end-capped polyesters.
  • the amount of the aliphatic diol or aliphatic polyol is 1-1.1 times the stoichiometric amount required for the preparation of the polyether-polyester.
  • one ester group of the di(C 1 -C 4 )alkyl ester of aromatic dicarboxylic acid is subject to the transesterification reaction directly building up the polymer instead of through the usual bis(diol or polyol)ester of the aromatic dicarboxylic acid (e.g. bis(hydroxyethyl) terephtalate).
  • bis(diol or polyol)ester of the aromatic dicarboxylic acid e.g. bis(hydroxyethyl) terephtalate.
  • the polyether is added in step (a).
  • the reaction temperature of step (a) is 180-270°C, preferably 190-230°C.
  • the inert solvent has a boiling point below or equal to the reaction temperature of step (a).
  • the inert solvent has a boiling point of 100-240°C, more preferably, 150-210°C.
  • the inert solvent is one or more selected from the group consisting of diethylene glycol di(C 1 -C 4 )alkyl ethers and dipropylene glycol di(C 1 -C 4 )alkyl ethers which are environmentally benign solvents.
  • the inert solvent is diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether or diethylene glycol diethyl ether.
  • the amount of the said inert solvent is 0.5-40% of the batch size of step (a), which can effectively prevent the di(C 1 -C 4 )alkyl ester of aromatic dicarboxylic acid from sublimation and does not slow down the reaction.
  • the inert solvent is removed by distillation under vacuum before or after step (b).
  • step (b) comprises sparging an inert gas into the reactant of step (b) at 180-230°C.
  • the inert gas is nitrogen, argon or carbon dioxide.
  • step (a) and step (b) are carried out in the presence of at least one transesterification catalyst.
  • the transesterification catalyst is one or more selected from the group consisting of organic titanium catalysts such as titanium tetraisopropylate, organic tin catalysts, calcium acetoacetonate, zinc acetate and calcium hypophosphite.
  • the di(C 1 -C 4 )alkyl ester of aromatic dicarboxylic acid is one or more selected from the group consisting of dimethyl esters, diethyl esters, dipropyl esters and dibutyl esters of orthophthalic acid, terephthalic acid, isophthalic acid, 5-sulfoisophthalic acid, 1,2-naphthalene dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedecarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acids.
  • the aliphatic diol is one or more selected from the group consisting of C 2 -C 12 aliphatic diols
  • the aliphatic polyol is one or more selected from the group consisting of C 3 -C 12 aliphatic triols.
  • the aliphatic diol is one or more selected from the group consisting of ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-decanediol, 1,2-dodecanediol and neopentylene glycol.
  • the polyether has an average molecular weight of 750-5000.
  • the polyether is one or more selected from the group consisting of:
  • the di(C 1 -C 4 )alkyl ester of aromatic dicarboxylic acid is one or more selected from the group consisting of dimethyl terephthalate, dimethyl isophthalate and dimethyl 5-sulfoisophthalate;
  • the aliphatic diol is one or more selected from the group consisting of ethylene glycol and 1,2-propylene glycol;
  • the polyether is one or more selected from the group consisting of:
  • the di(C 1 -C 4 )alkyl ester of aromatic dicarboxylic acid is dimethyl terephthalate;
  • the aliphatic diol is one or more selected from the group consisting of ethylene glycol and 1,2-propylene glycol;
  • the polyether is one or more selected from the group consisting of MPEG of MW 750, PEG of MW 600, PEG of MW 1000, PEG of MW 1500, MPEG-b-PPG of MW 750, PPG-b-PEG-b-PPG of MW 1000 and PPG-b-PEG-b-PPG of MW 1500, where MPEG is methoxy polyethylene glycol, PEG is polyethylene glycol, PPG is polypropylene glycol.
  • the polyether-polyester block copolymer produced by the process of the present invention can be used as soil release agent.
  • DMT dimethyl terephthalate
  • PG 1,2-propylene glycol
  • K acetate potassium acetate
  • MPEG-750 polyethylene glycol monomethyl ether of molecular weight 750
  • DEG-di-Et diethylelene glycol diethyl ether
  • TPT titanium tetraisopropylate
  • the charges of raw materials are listed in Table 1.
  • the reaction was carried out at 205-215 °C with stirring and nitrogen sparge as indicated in the table while collecting methanol by-product.
  • the reaction was continued at the reaction temperature until C-13 NMR showed completion, which took 12 to 36 hours under N 2 sparge.
  • Diethylene glycol diethyl ether could be removed after 7-12 hours of reaction under vacuum, and the reaction was then continued under nitrogen sparge or under vacuum till completion. After the reaction, the mixture was cooled to room temperature to yield the product.
  • Example 3 Same process as Example 3 was followed except that 1.0 grams of ethylene glycol was added to the reaction charges as listed in Table 1.
  • Methyl poly(ethylene glycol)-b-poly(propylene glycol) (MW 750 with 2 mole of propylene glycol) was used instead of MPEG.
  • the charges are listed in Table 2. Procedure of Example 3 was followed.
  • Methyl poly(ethylene glycol)-b-poly(propylene glycol) (MW 750 with 1 mole of propylene glycol) was used instead of MPEG.
  • Calcium acetonacetonate and Tyzor TPT were used to push the reaction. The charges are listed in Table 2. Procedure of Example 3 was followed.
  • Triblock polyglycol of poly(propylene glycol)-b-poly(ethylene glycol)-b-poly(propylene glycol) (PO-EO-PO, MW 1000 with 2 moles of PO) was used instead of methyl polyethylene glycol.
  • PO-EO-PO poly(propylene glycol)-b-poly(ethylene glycol)-b-poly(propylene glycol)
  • Triblock polyglycol of poly(propylene glycol)-b-poly(ethylene glycol)-b-poly(propylene glycol) (PO-EO-PO, MW 1000 with 3 moles of PO) was used instead of methyl polyethylene glycol.
  • PO-EO-PO poly(propylene glycol)-b-poly(ethylene glycol)-b-poly(propylene glycol)
  • Triblock polyglycol of poly(propylene glycol)-b-poly(ethylene glycol)-b-poly(propylene glycol) (PO-EO-PO, MW 1500 with 2 moles of PO) was used instead of methyl polyethylene glycol.
  • PO-EO-PO poly(propylene glycol)-b-poly(ethylene glycol)-b-poly(propylene glycol)
  • Triblock polyglycol of poly(propylene glycol)-b-poly(ethylene glycol)-b-poly(propylene glycol) (PO-EO-PO, MW 1500 with 2 moles of PO) was used instead of methyl polyethylene glycol.
  • PO-EO-PO poly(propylene glycol)-b-poly(ethylene glycol)-b-poly(propylene glycol)
  • Polyethylene glycol of the specified molecular weight was used instead of MPEG, together with ethylene glycol or/and propylene glycol.
  • Raw material charages are listed in Table 4. Procedure of Example 3 was followed and the reaction was done at 215 °C.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Polyesters Or Polycarbonates (AREA)

Claims (14)

  1. Ein Verfahren zur Herstellung eines Polyether-Polyester-Blockcopolymers, umfassend:
    (a) Umesterungsreaktion mindestens eines Di(C1-C4)alkylesters einer aromatischen Dicarbonsäure mit mindestens einem aliphatischen Diol oder aliphatischen Polyol in einem inerten Lösungsmittel, wobei das inerte Lösungsmittel einen Siedepunkt aufweist, der höher ist als der Siedepunkt des Alkohol-Nebenproduktes der Umesterungsreaktion, und wobei das inerte Lösungsmittel eines oder mehrere, ausgewählt aus der Gruppe bestehend aus Diethylenglycol-di(C1-C4)alkylethern und Dipropylenglycol-di(C1-C4)alkylethern, ist;
    (b) Polykondensationsreaktion des Produktes aus Schritt (a) und mindestens eines Polyethers, wobei der Polyether mindestens eine endständige Hydroxygruppe aufweist.
  2. Das Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass die Menge des aliphatischen Diols oder aliphatischen Polyols 1-1,1-mal der stöchiometrischen Menge entspricht, die für die Herstellung des Polyether-Polyester-Blockcopolymers erforderlich ist.
  3. Das Verfahren gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, dass der Polyether in Schritt (a) hinzugefügt wird.
  4. Das Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Reaktionstemperatur von Schritt (a) 180-270 °C, bevorzugt 190-230 °C, beträgt.
  5. Das Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das inerte Lösungsmittel einen Siedepunkt aufweist, der niedriger als oder gleich wie die Reaktionstemperatur von Schritt (a) ist, bevorzugt 100-240 °C, stärker bevorzugt 150-210 °C.
  6. Das Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das inerte Lösungsmittel Diethylenglycol-dimethylether, Dipropylenglycoldimethylether oder Diethylenglycol-diethylether ist.
  7. Das Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Menge des inerten Lösungsmittels 0,5-40 % der Batchgröße von Schritt (a) beträgt.
  8. Das Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das inerte Lösungsmittel vor oder nach Schritt (b) durch Destillation unter Vakuum entfernt wird.
  9. Das Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass Schritt (b) ein Durchperlen eines Inertgases, bevorzugt Stickstoff, Argon oder Kohlendioxid, durch den Reaktanten von Schritt (b) bei 180-230 °C umfasst.
  10. Das Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass Schritt (a) und Schritt (b) in Gegenwart mindestens eines Umesterungskatalysators durchgeführt werden, wobei ein oder mehrere des Umesterungskatalysators vorzugsweise aus der Gruppe bestehend aus Titantetraisopropylat, Calciumacetoacetonat und Calciumhypophosphit ausgewählt sind.
  11. Das Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Di(C1-C4)alkylester einer aromatischen Dicarbonsäure einer oder mehrere, ausgewählt aus der Gruppe bestehend aus Dimethylestern, Diethylestern, Dipropylestern und Dibutylestern von Orthophthalsäure, Terephthalsäure, Isophthalsäure, 5-Sulfoisophthalsäure, 1,2-Naphthalendicarbonsäure, 1,4-Naphthalendicarbonsäure, 1,5-Naphthalendicarbonsäure, 1,6-Naphthalendicarbonsäure, 1,7-Naphthalendicarbonsäure, 1,8-Naphthalendicarbonsäure, 2,3-Naphthalendicarbonsäure, 2,6-Naphthalendicarbonsäure und 2,7-Naphthalendicarbonsäuren, ist.
  12. Das Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das aliphatische Diol eines oder mehrere, ausgewählt aus der Gruppe bestehend aus C2-C12-aliphatischen Diolen ist, das aliphatische Polyol eines oder mehrere, ausgewählt aus der Gruppe bestehend aus C3-C12-aliphatischen Triolen, bevorzugt aus der Gruppe bestehend aus Ethylenglycol, 1,2-Propylenglycol, 1,3-Propylenglycol, 1,2-Butylenglycol, 1,4-Butylenglycol, 1,5-Pentandiol, 1,6-Hexandiol, 1,8-Octandiol, 1,2-Decandiol, 1,2-Dodecandiol und Neopentylenglycol, ist.
  13. Das Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Polyether einer oder mehrere, ausgewählt aus der Gruppe bestehend aus:
    (1) Polyethylenglycol, Poly-1,2-propylenglycol, Poly-1,3-propylenglycol und Copolymeren davon; und
    (2) Mono(C1-C4)alkylethern der Polyether aus (1) ist.
  14. Das Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Di(C1-C4)alkylester einer aromatischen Dicarbonsäure einer oder mehrere, ausgewählt aus der Gruppe bestehend aus Dimethylterephthalat, Dimethylisophthalat und Dimethyl-5-sulfoisophthalat ist; wobei Dimethylterephthalat bevorzugt ist;
    das aliphatische Diol eines oder mehrere, ausgewählt aus der Gruppe bestehend aus Ethylenglycol und 1,2-Propylenglycol, ist;
    und der Polyether einer oder mehrere, ausgewählt aus der Gruppe bestehend aus:
    (1) Polyethylenglycol, Poly-1,2-propylenglycol und Blockcopolymeren davon; und
    (2) Mono(C1-C4)alkylethern der Polyether aus (1) ist,
    wobei der Polyether bevorzugt aus der Gruppe bestehend aus MPEG mit MW 750, PEG mit MW 600, PEG mit MW 1000, PEG mit MW 1500, MPEG-b-PPG mit MW 750, PPG-b-PEG-b-PPG mit MW 1000 und PPG-b-PEG-b-PPG mit MW 1500 ausgewählt ist.
EP09846687.3A 2009-07-01 2009-07-01 Verfahren zur herstellung von polyether-polyester-blockcopolymer Active EP2448992B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2009/072575 WO2011000158A1 (en) 2009-07-01 2009-07-01 Process for producing polyether-polyester block copolymer

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EP2448992A1 EP2448992A1 (de) 2012-05-09
EP2448992A4 EP2448992A4 (de) 2013-01-09
EP2448992B1 true EP2448992B1 (de) 2014-04-30

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US (1) US8779084B2 (de)
EP (1) EP2448992B1 (de)
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WO (1) WO2011000158A1 (de)

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EP2448992A1 (de) 2012-05-09
CN102482405B (zh) 2014-06-04
WO2011000158A1 (en) 2011-01-06
CN102482405A (zh) 2012-05-30
US8779084B2 (en) 2014-07-15
EP2448992A4 (de) 2013-01-09
US20120059185A1 (en) 2012-03-08

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